Printing textiles with pigments



Patented Apr. 4, 1944 PRINTING TEXTILES WITH PIGMEN'I'S Willard L.Morgan, Edgewood, and Norman L. Vaughn, Providence, R. 1., asalgnorstoArnold, Hoffman & Co. Incorporated, a corporation of Rhode Island NoDrawing. Application June 21, 1941,'

Serial No. 399,230

3 Claims. (01. 106-170) This invention relates to the printing oftextiles in colored patterns wherein the coloration is secured bypigments which are applied in and fastened to the cloth in a washresistant manner by means of an emulsion of a new and novel composition.

The printing of textiles as normally practiced comprises essentiallylocally dyeing areas in order to secure desired designs. The dyestuflsolution is applied to the cloth by passage of the cloth past anintaglio engraved roll, from which the cloth picks-up the dyestuffsolution. In order that suflicient quantity may be picked up and that itshould not spread, it is essential that the dye stuff solution bethickened to a very heavy paste.

This thickening is usually secured by the use of thick, heavy boiledstarch pastes or by natural gum pastes, but the use of these materialsinterferes seriously with the securing of a high degree of sharpnessAfter the goods have been printed and dried, it is necessary that theybe put through various steamings, aging operations, or other specialtreatments to cause the dyestufl. to penetrate into the fibers or tochemically alter the nature of the dyestuif in order to secure thefixation on the cloth. This makes it very diflicult and expensive. tocontrol shades and the printer never knows exactly what his work willlook like until it has been put through a great many op-v erations andsubsequently washed, inasmuch as not all of the dyestuif is ever fixedto the cloth, and furthermore the thickener stiflens the cloth and mustbe removed from the fabric. Faulty printing and losses may occur atquite a number of steps and may reach serious proportions before it isdiscovered in later operations. Even after the goods have been washed inorder to wash off starches and gums from the cloth, it is often foundthat these cannot be removed sufliciently and desizing operations arethen applied in the case of cotton goods. In the case of printing onrayon, it is impossible to print with most of the commercial starchesinasmuch as they cannot be removed from the rayon sufliciently and canonly be removed by prolonged washing which with the light rayon fabricsis suflicient to distort the goods and cause severe damage.

In a copending application by one of the joint inventors of this case,Serial Number 386,627, filed April 3, 1941, it is shown that the nsectsoaps and suspended water-insoluble, solid fatty materials give pasteswhich are ideally suited for printing textiles in that they present asmooth, heavy body and after being printed on the fabric,

any stiffness where the goods ar printed, thus it is possible to omitwashing operations after printing in most cases.

We have found that pastes thickened by soaps and with suspendedwater-insoluble, solid fatty materials can be used to emulsify lacquersor solvents carrying binding resins or cellulose ester or ethercompositions and that such compositions when pigmented are highlysuitable for printing onto textiles and that color prints are, therebysecured which show excellent fastness to washthey do not affect thehandle and do not cause to ing and dry cleaning, a good resistance torubbing, and a lack of stiflness or change in handle where the goods areprinted. As most pigments are very fast to light, their use inthismanner is attractive. The use of our emulsions ofl'er a great manyadvantages to the printer. One of the most important advantages is thatas soon as the goods are printed and come from the printed roll, thefinal shade and its completeness of coverage are immediately visible sothat any defectiveness in work is immediately caught without anyproduction of faulty goods.

Our printing pastes are printed from ordinary textile intaglio printingrolls. The use of our printing method is particularly attractive becauseof its simplicity, since as soon as the goods are printed and run overthe dry cans, the cloth can be considered as finished, there bein nonecessity of further treatment to set the color such as occurs wheredyes are used, and there is no necessity of washing out the goodssuch asis necessary where starches are used. The goods as they come off the drycans are uniformly soft across the face, the paste having no stiffeningeffect whatsoever. This greatly simplifies printing and cheapens thecost of textile printing as well as diminishing serious rejectionsbecause difficulties are quickly caught in the first step of printing.

As our emulsions are dispersions of lacquer in a continuous water phase,it is very easy to clean this off of the machinery when it is desirableto change colors as the composition dilutes with water. Due to its highstability it does not coagulate or leave any stickiness on the printedroll, and it cleans out of the engraving quickly and completely. As ourpastes dilute readily with water, it is possible to add at any timepigments dispersed in water. The use of our emulsion gives very sharpprints as the pigments, even when added in the form of water-dispersedpastes, appear to attach themselves to or to enter into the lacquerphase; and as the cloth is first wetted by the continuous or waterphase, the colored oily lacquer shows no tendency whatsoever to spreador men the adjacent wet cloth. Our printing paste gives extremesharpness which has never been secured by the use of starches or naturalgums as printing vehicles. The pastes are very stable and may be keptfor long periods and are not subject to bacterial attack as is true ofthe usual starches and gum thickeners. On the printing machine theextremely high stability permits the machines to run continuouslywithout danger of the emulsions changing character or coagulating.

Pigmented emulsions employing water emulsified or dispersed in anexterior lacquer phase have been mployed for printing textiles. Suchemulsions have shown many difiiculties in use. Where a lacquer ispresent as an exterior continuous phase, the printing paste isessentially the same as a lacquer in nature and is inflammable andwhatever parts of the printing machines which come into contact with thesolvents are immediately wet by the same, thus such emulsions when usedin commercial printing machines have destructive action on the rubberblankets used in the machines since the solvents come in direct contactwith the rubber and swell the same with rapid disintegration following.Likewise, this same type of lacquer emulsions irritate the human skinwhen they come into contact with the same. With water as the externalphase in our emulsions we eliminate all of the above difliculties.Furthermore, if the attempt is made to add pigments dispersed in water,which is the normal way pigments are sold, to an emulsion having acontinuous lacquer outer phase, the pigments will not mix in and thesame is true if water is added since then water is essentially beingadded to an oily material. In consequence, the preparation of anemulsion printing paste with lacquer continuous phases involvescomplicated emulsifying machinery in order to beat in and atomizethoroughly the pigments and the water mixed in the ordinary dilutions,especially as it is desirable to add water for obvious economic reasons.Unless this job is done carefully, the emulsions show spottiness andincomplete coverage results when printed and where the dispersion isalso not very good, the emulsion will soon break under the continuousagitating action of the printing roller dipping in the pan of color. Incontrast, our new mulsion pigment printing media has a water exteriorphase and, as such, water-dispersed pig-. ment pastes may be addeddirectly and merely stirred in without any special kind of apparatus.That our printing pastes are similar in many respects to a water pasteis easily demonstrated by passing an electric current through our pastein series with an electric light. Our paste will conduct an electriccurrent and light the light just as will a soap solution, whereas thepigmented emulsions which have, up to now, been employed in the textileprinting art will not, as these have an oily outer continuous phase. Aswill be shown later, our pastes are extremely stable by reason of thevery large amounts of stabilizer and dispersing agent used, and at notime is mechanical machinery necessary for the emulsiflcation, the samebeing completely secured by hand if desired, giving globules of aboutone micron size.

The use of a lacquer dispersion in water as a printing paste is notnormally possible due to the thinness generally found with suchemulsions. It is only when the dispersed phase approaches -75% of thetotal liquid and is highly dispersed that the emulsion begins to show ahigh viscosity at all suitable for use as a printing paste. The use ofsuch large amounts of lacquer, however, as an internal phase isobviously uneconomic as against printing where the lacquer is theexternal phase and need only be present to the extent of 25%. Thus,three times as much solvent would be necessary, and beside the addedburden of cost the evaporation of such'large volumes of solvent into theprinting room atmosphere causes a very severe nuisance. In the securingof satisfactory sharp printing emulsions having a continuous water phaseshowing all the advantages of such emulsions, it was thus obviouslyeconomically necessary to find a means of securing thick pastes withoutthe use of large internal dispersed lacquer phases.

It is an object of this invention to prepare printing emulsions havingan exterior water phase useful as compositions for textile decorationwhich are inexpensive, involving a minimum of solvents, which emulsionsare extremely stable.

It is a further object of this invention to provide a means of pigmentprinting on textiles which will give wash resistance and dry cleaningresistant prints.

We have found that by using high amounts of .soap or soaps and suspendedfatty-materials in the water phase of our emulsions that we can secureoil in water emulsions which are suitable as cheap thickeners forprinting and in which lacquer phases may be very simply emulsified, thusgiving us cheap, stable emulsions suitable for printing of textiles withpigments. We have also found that the use of soaps in this manner doesnot hinder the deposition of the pigment on the cloth as the paste isdried out and does not affect thewash resistance of the depositedpigment adversely as one would expect from such powerful detergents assoaps. The wash resistance of prints made with our pigment pastes isvery satisfactory. Furthermore, the use of soaps as a thickener does notgive stiff deposits in the cloth, but rather leaves the cloth in a verysoft and pleasing handle such that the printed portions feel as flexibleas the unprinted portions. The printed cloth is highly water absorbentand in its soft printed condition can be used directly, and washingoperations may be eliminated.

Thin printing inks for paper have been made which have used smallamounts of soap as emulsifiers, but in insufficient quantity for thesoaps to provide any thickness to the printing emulsion. Consequently,in both the paper and the textile printing arts, up to date, theemulsions used have been preferably of the water dispersed in oil typesolely because in this type a minimum of solvent or lacquer phase couldbe used readily. Whenever the dispersed internal phase approached 75%,the globules then become so closely packed that they press closely oneupon an-.

other and the separating films of the continuous phase become extremelythin. Under these conditions only do emulsions of two thin liquids showany desired thickness approaching a thick paste. With water as theinternal phase this condition is easily secured under economicconditions, but to use 75% of lacquer as an internal phase isuneconomic. We secure still, and it is one of the objects of thisinvention to prepare stiif, thickened pastes, with lacquer as theinternal phase where the percentage of lacquer or internal phase neednot exceed 50% and may be as low as 20% or less. We are able to securethick, heavy pastes which are oil in water emulsions with thisrelatively low internal phase volume of the lacquer.

lacquer or solvents by the use of an external phase which carries watersoluble soaps in a reiatlvely large percentage so that our externalaqueous phase is of heavy viscosity. This water phase may carry inaddition to soaps, suspended solid, insoluble fatty materials whichfurther thicken the aqueous phase.

We prefer to use the water-soluble soaps of the fatty acids, such as,lauric acid, palmitic acid, 'stearic acid, and oleic acid with thealkalies, sodium, potassium, ammonium, borax or the organic bases suchas ethylene diamine, trie'thanolamine and the other ethanolamines. Thesoaps are used in relatively large amounts, the amounts being present inthe final printing paste being in excess of 3%. It is obvious that amuch higher percentage of soap is actually present'in the water phase.We find that an excess of fatty material is desirable over that combinedwith alkali for best stability and thickening value. We prefer to use incombination with our soaps, solid fatty substances, insoluble in water,such as, beeswax, Japan wax, solid fatty glycerides, glycerylmonostearate, and hydrogenated solid fatty esters; solid fatty acids,such as, stearic acid, palmitic acid, or mixtures of the same or solidhydrogenated fatty acids, and the solid glycol esters with the fattyacids, such as, diethylene glycol distearate, diethylene glycolmonostearate, and propylene glycol monostearate.

The use of soaps as thickeners in printing pastes would be expected tobe attended with the difficulty of foaming, and in some cases ouremulsified lacquers show this tendency, but we have discovered that whenour paste carries suspended fatty solid material that the latter act asantifoaming agents. We may also add other antlfoaming agents such as,terpineols, pine oil, kerosene, naphtha, cr'octyl alcohol. The use ofone or more of these materials is generally desirable and we addsufficient to our paste to prevent such troubles. In connection with theuse of our fatty substances, we may use small quantities ofantirancidity agents where desirable, such agents being those which arewell known, and by preference we may use isothymol or the ethyl estersof parahydroxy benzolc acid.

From the standpoint of cheapness, we prefer to use as solvents in ourlacquers those preferably of low cost; namely, ordinary hydrocarbonsolvents. Some of these, such as, kerosene also have the advantage ofpreventing foaming. The choice of solvents to be used is also dependentupon the binders or lacquer resins to be used as these mostly have to bedissolved in the solvents. We have found terpineol or pine oil tofrequently be very useful in this respect because of its cheapness andwide solvent powers as well as its anti-foaming properties. In general,we have found that solvents which are water soluble must be avoidedwhere the binder is water insoluble since the use of such compositionsresults in immediate precipitation. Generally we find the addition ofwater-soluble solvents also has a thinning effect upon our emulsionpaste. Preferably, then, we use solvents which are water insoluble andwhich are good solvents for the lacquer cellulosic bases or resin baseswhich are to be employed as binders for the pigments. Where mixtures ofsolvents are employed it is preferred that the active solvent should beof slightly higher boiling point than the diluents so that the lastsolvent to evaporate remains a good solvent for It is preferred that thesolvents should have a boiling point above that of water so that after.printing, the water is first removed by drying, leaving local depositsof-thelacquer which thereafter proceed to dry to auniform deposit withno precipitation difllculties. As would naturally be expected, the useof lacquer phases which are heavy and thick impart to the final printingpastes a somewhat higher viscosity, but it is impossible to secure athick printing paste with 50% or'less internal lacquer phaseirrespective of its viscosity if insuflicient soap is used in the waterphase. That is, it is very important that the water phase must be veryhigh- 1y thickened.

As binders for fastening the pigments to the cloth, we may use materialssoluble in either the solvent or the water phases. We may use lacquerscomposed of solvent solutions of ethyl cellulose, cellulose esters, suchas, cellulose nitrate, cellulose acetate, or mixtures of these withresins and plasticizers. We may also use solvent solu-- tions of alkydresins, natural resins such as dammar, or the urea formaldehyde typeresins or mixtures of these various resins with plasticizers whereadditional flexibility is necessary. We may also use the water-solubleurea formaldehyde resins dissolved in our aqueous phase in which caseafter printing and drying our cloth, we prefer that the cloth should bebaked to further set the resin and make it thereafter water insoluble.Where we use a water-soluble, urea-formaldehyde resin, it is preferredthat the soaps be used as thickeners should be ammonium soaps as the useof other soaps involving fixed alkalies interfere with the fixation ofthe resin.

Of the various binders we prefer to use ethyl cellulose as this materialshows a maximum of flexibility and toughness. It is found that alsowhere most other binders must be used to the extent of at least twoparts for every one part of pigment solids employed, that only one partof ethyl cellulose is necessary to secure very good binding actionsufiicient to resist ordinary washing tests. We have found that ethylcellulose prepared with an ethoxy content of 46.8 to 48.5% shows amaximum resistance to washing and we prefer the use of this material inany of the commercial viscosities available, but prefer to use thehigher viscosity types such as the viscosity. We may use the other typesof ethyl cellulose of other degrees of ethylation, and we have foundthat the use of an ethyl cellulose of 43.5 to 44.5% ethoxy content, oreven less, gives a maximum resistance to dry cleaning, and we may employthis type where the textile to be printed will be subject to suchmethods of cleaning. For gen.- eral all around use showing a maximumresist- 'ance to both washing and dry cleaning, we prefer to usemixtures of these two types.

Printing pastes which are suitable for printing pigments onto textilesin accordance with our invention may be prepared in several ways. Ineach case we first dissolve the binding resin or cellulosic compound inthe solvent for the same and in some cases we have found it possible toproduce homogeneous solutions containing, in addition, at most, smallquantities of water and the soaps dissolved along with the solvents andthe lacquer ingredients. Such products containing our lacquer binderingredients and our soaps for thickenportion of solvent carrying nobinder. This solvent solution containing either none or at mostsmallamounts of water may then be diluted with larger volumes of water andgive thick, stable emulsion pastes upon simple stirring. The pastes thusproduced maybe used as diluents or extenders for the pastes produced bythe first method. It is perfectly obvious that the solvent solution ofsoap may also 'be blended with the lacquer soap solvent combination andthereafter diluted directly with water to form an emulsified paste.Perhaps one of the simplest ways of making our pastes is to merelydissolve the lacquer binding ingredients comprising the cellulosiccompounds or resins in their active solvent and thereafter to add thediluting solvents while at the same time preparing an aqueous solutionof soaps to the desired extent. The lacquer solution is then stirredinto the thick soap suspension directly to again form an emulsion. Inthe fourth method, the fatty acids may be dissolved in the lacquersolvent solution and this may be stirred into an aqueous solution ofalkali containing suflicient alkali to convert and form the desiredamount of soaps. In any of these methods it is found that simplestirring suflices to produce a very stable emulsion, and in general itis found that in the thick pastes, the dispersed globules of solvent orlacquer phase are generally all around one micron in. diameter.

The methods of making our emulsions will be more specifically detailedin the examples which follow.

It is apparent that as our emulsions are oilin-water type that waterpastes of the ordinary textile thickeners such as starch pastes andnatural gum pastes can be directly mixed with our emulsion thickenerswhich is impossible with emulsions of the water-in-oil type.

The pigments which may be used in our pastes as a means of printing maybe insoluble metallic compounds such as titanium dioxide, zinc oxide,carbon black, yellow lead chromate, ultramarine, or they may be complexorganic pigments such as the phthalocyanine compounds such as the'Monastral blue and green pigments, or they may be-other insolubleorganic pigments such as the insoluble azo naphthol compound such aspara red or even insoluble oxidized vat color pigments. For use with ourprinting pastes, it is preferred that these pigments be ground anddispersed as water pastes as they are commonly supplied in the marketfor. their various uses. Pigment pastes which are ground in oil can alsobe used, but these. ordinarily must be emulsified into our pastes by theuse of emulsification machinery. Oil dispersed pigment pastes can beadded directly to our concentrated lacquer and soap base compositionsbefore they are emulsified. Our preferred method of introducing thepigments is to add the water dispersed pigment paste directly to ourprinting paste emulsions after they have been slightly diluted withwater so that they will stir in readily. Our emulsions may be used toprint ordinary dyestuffs onto cloth in which case the dyestuff is merelydissolved in the water used in making the emulsion pastes.

It is found that when our pigmented printing pastes are examined underthe microscope that in general the pigments are preferentially wet bythe lacquer phases and are either found in the lacquers or at theinterface.

It is found that the viscosity of our printing paste emulsions can beregulated to any desired thickness by merely adding further water to anygiven paste, or if additional thickness is desired.

' by adding more of the soap suspension or of the concentratedsoap-lacquer base. The addition of small quntities of alcoholsor otherwater-soluble solvents can be employed to reduce the viscoslties- Aconcentrated lacquer and'soap base may be prepared by dissolving 5 partsby weight of 100 centipoise viscosity ethyl cellulose of 48.8 to 48.5%ethoxy content in 74 parts of pine oil and 12 parts pf oleic acid. Aftersecuring a clear solution, a caustic soda solution comprising 1.6 partsof sodium hydroxide and 7.4 parts oi. water are stirred in. ,The excessoleic-acid over that necessary for forming a soap aids in securing aclear, compatible solution mixture. The clear fluid solution may beshipped directly to textile printing mills and when desired for use bydiluting with water there is formed the thick printing paste emulsion.In order to form the thick emulsion printing paste to 100 parts of thislacquer, we may add 95 parts of water with simple stirring. A paste isformed which increases in viscosity as more and more of the water isstirred in and shows a'maximum body beyond which further addition'ofwater causes a thinning. As the 'water is' stirred in, there is produceda smooth, heavy, paste comprising an oil-in-water type emulsion. Thispaste is quite heavy and shows little tendency to flow. To the creamypaste we may then add, for example, 20

parts of Monastral Fast Blue BF pigment paste (E. I. du Pont de Nemours81 Co., Inc.) which paste will contain approximately four parts ofpigment solids. The pigment printing color is then ready for use and maybe applied to the printing color boxes on the ordinary intagllo textiletype printing machine, and it may be printed alongside of other types ofcolors and dyestuffs. Cloth such as x 80 cotton cloth may be run throughthe printing machine and after drying on cans to remove the water andsolvent the cloth is ready for use, if only our type pigment printingcolors have been used thus avoiding the aging and washing treatmentwhich are attendant upon the use of the ordinary dyestuffs printed withstarch pastes. Designs printed in this way are very sharp andexceptional in their flne line reproduction. Prints secured with thispaste were exceedingly good to washing. Printing runs with the emulsionshowed no tendency to foam and long continuous runs of over 25,000 yardsshowed no tendency for the emulsion to break down or to coagulate. Thestability of the emulsions were such that after three months storagethere were no changes in the thickness orin the particle size of theemulsions. The emulsion paste as printed contained 41.5% of dispersedinterior lacquer phase. The paste also contained 5.9% soap and theexterior water phase contained all of the soap as a solution of 10.2%sodium ole'ate.

Erample 2 To 43 parts of pine oil and 20 parts of the petroleumhydrocarbon distillate boiling between 310-390 F., boiling points(Varsol, Colonial Beacon Co.) we added 12 parts of oleic acid and 2.43parts of 28% concentrated ammonia. A separate water solution wasprepared which contained 70 parts of water and 12 ports of awater-soluble urea-formaldehyde resin. This aqueous solution of binderwas then stirred into the soap and solvent mixture and a thickoil-in-water type emulsion formed which was suitable as a, printingpaste. There was next stirred in 13 parts of Monastral Fast Blue BFpigment paste. The mixture was a stable, thick printing emulsion whichwas printed on cotton and dried on cans to remove the solvent andthereafter baked for three minutes at 300 F. to set the resin. Theprinted cloth was soft, sharply printed and resistant to dry cleaningand washing. The emulsion as applied to the printing machine had asolvent interior phase of 38% and an outer aqueous phase which containedll.3% soap dissolved in the.water or 6.9% ammonium oleate in the entiremixture.

Example 3 A concentrated lacquer and soap base may be prepared by addingto 70.5 parts of pine oil, 11d parts of oleic acid and five parts of.diethylene g ycol monostearate. In this mixture 'there are dissolved4.75 parts of 100 centipoise ethyl cellulose of 46.8 to 48.5% ethoxy'content. After the ethyl cellulose is dissolved, a caustic sodasolution containing 1.25 parts of sodium hydroxide and 6.83 parts ofwater were then stirred in. The alkali is insuflicient to convert allthe oleic acid into soap. This gives a mixture which' may be shipped tothe textile printing mills and then diluted with water to form theprinting emulsion. In order to form a printing paste emulsion there ariaadded to 100 parts of this base mixture 120 parts of water which may bestirred in readily by hand or by paddles to form a smooth, heavy, creamypaste which is suitable for pigment printing. This paste would thencontain 34.5% internal lacquer phase and a total of 5.56% sodium oleatesoap. The aqueous phase would be a solution of il sodium oleate soap andin addition to the dispersed lacquer phase there would be some dispersedwater insoluble diethylene glycol monostearate present.

Example 4 A. solution of 20 parts of pine oil and 13.3 parts of oleicacid was used to dissolve three parts of ethyl cellulose to form a clearlacquer solution. There is then stirred into this lacquer a causticsolution to form an emulsion paste directly, thus a caustic solutioncontaining 1.9% parts of sodium hydroxide and 61.8 parts of water may bestirred into the lacquer and there is formed directly a dispersion ofthe lacquer in the water phase as a very heavy emulsion paste which issuitable for printing pigments. The paste thus formed contains only23.1% internal dispersed lacquer phase. The mixture contains 15.3%sodium oleate which gives a concentration of 19.9% soap in the waterphase.

Example 5 A concentrated lacquer and soap base suitable for shipment maybe first prepared by mixing 43 parts of pine oil and 12 parts of oleicacid with 5 parts of 50 centipoise ethyl cellulose, 43.5 to 44.5% ethoxycontent. After the ethyl cellulose has dissolved, 34 parts of a lighthydrocarbon solvent of boiling point range from 315 to 387 F.

in. The base up to this point contains 12.18% soap, 5% binder, 77%lacquer solvents, .70% oleic acid, 5.12% water. The slightly heavysolution produced may then be shipped to the point of use andwhen'desired to make a printing paste, there is added to 100 parts ofthis base 70 parts of water and 10 parts of ethyl alcohol. This'gives asmooth, heavy paste on simple stirring which is quite stable. In orderto secure a yellow print there may be then added 30 parts of HanzaYellow GDL pigment paste (15.75% solids) (General Dyestufl Co.) Afterstirring the pigment in well, the paste is ready for printing. Thispaste is somewhat thinner than would be the case of we used water inplace of the ethyl alcohol. When printed onto cotton cloth and dried onordinary .textile steam cans to remove the solvents, the

printed cloth was found to be very resistant to dry cleaning solventsand to washing. This paste as printed, contained 41.7% internal lacquerphase. There was present in the mixture 6.1% sodium oleate soap whichamounts to 10.4% soap in the water phase.

Example 6 7 completely dissolved, 34 grams of the light pe- (GulfSolvent G-Gulf-Oil Corp.) are added and acid, 5.12% water.

troleum hydrocarbon solvent used in Example 5 are then added and then acaustic soda solution containing 1.6 parts by weight of sodium hydroxideand 4.4 parts by weight of water are stirred in. This gives aconcentrated lacquer and soap phase of a. heavy fluid consistency whichis a solution, and it may be shipped without difliculty. The base up tothis point contains 12.18% soap, 5% binder, 77% lacquer solvents, .70%oleic When it is desired to make an emulsion suitable for printing fromthis base, there is added to parts by weight of this base parts byweight of water. To the thick creamy paste thus produced there arestirred in 20 parts by weight of Monastral Fast Blue BF pigment paste.This gives a printing paste which while thick enough for .printing maybe considered slightly thin by some printers. and in some cases aprinter may desire the same to be thicker. The paste may be reduced incost and increased in thickness by homogenizing into it 50 parts more byweight of the light petroleum solvent used in Example 5 (Gulf SolventB). A smooth printing paste thus secured when printed from intagliorolls onto cotton cloth gives prints which after drying on the cans toremove the solvents are very highly resistant to washing and drycleaning. The final pigment paste formed in Example 7 A soap and lacqueremulsion base was first formed by preparing the following solution.After 11 parts by weight of stearic acid and 4.5 parts of 100 centipoiseethyl cellulose oi 46.8% to 48.5% ethoxy content have been dissolved in75 parts by weight of pine oil 'an alkaline solution containing 2.11parts by weight of monoethanolamine and 7.39 parts by weight of waterare mixed in. This clear lacquer solution base may be shipped, and whenit is desired to form a printing paste we take 100 parts of this baseand stir into it 90 parts by weight of water. As we stir the water intoour concentrated base, the same becomes white and progressively heavy asthe water is stirred in, soon forming a very thick stable paste which isfound to .be an emulsion of the lacquer in the water. In order to makered prints we may add to the 190 parts of printing paste thus formed 30parts by weight of Lithosoi Fast Scarlet RF pigment paste, (13% solids,E. I. du Pont de Nemours) The red pigment paste is stirred in to form a,smooth, uniform pigment color. In order to extend and cheapen the pastewhile still maintaining approximately the same printing viscosity, wemay mix with this paste another emulsion printing paste which does not.

contain any binder. For example, we add 200 parts of a printing emulsionmade by stirring together 5.52 parts by weight of oleic acid, 36.85parts by weight of alight petroleum hydrocarbon solvent (Gulf SolventB), '57 parts by weight of water and dissolved in the water 0.63 part byweight of sodium hydroxide. This latter emulsion will be found to beequally as heavy as the first one discussed above, and the two may bereadily mixed in any proportion. In the proportions suggested the finalprinting paste would. comprise of 38.2% internal dispersed lacquer andsolvent phase and there would be present a total of 8.5% soaps in thewater phase. In the entire mixture the soaps would amount to 5.2%, being2.8% monoethanolamine stearate and 2.4% sodium oleate.

Example 8 A base product suitable for shipment to printing plants may bereadily prepared in a semisolid form which presents advantages from thestandpoint of shipments as contrasted to the liquid bases previouslydescribed. In this example, there is illustrated the use of a mixture offatty acids, namely, stearic and oleic acid which may be deliberatelymixed, or we may preferably use the commercial high titer red oil'whichis a mixture of stearic and oleic acid.

In 43 parts by weight of pine oil and 12 parts by weight of 28-30 titerred oil are dissolved by warming 2.5 parts by weight oi 50 centipoiseethyl cellulose, 43.5 to 44.5% ethoxy content and 2 parts by weight of100 centipoise ethyl cellulose, 46.8 to 48.5 ethoxy content. This mix isthoroughly dissolved and 34 parts by weight of the light hydrocarbonmentioned previously as Gulf Solvent G is added while still warm. A

caustic solution containing 4.4 parts by weight of stirred in. Theprinting paste contains 5.82%

sodium stearate and oleate soaps or 9.68% soap in the water phase. Theinternal lacquer phase was 39.9%.

Example 9 A concentrated lacquer and soap base was prepared bydissolving together 11.87 parts by weight of stearic acid, 4.86 partsethyl cellulose, 81 parts of pine oil, and 2.27 parts ofmonoethanolamine. To 100 parts of this paste 90 to 130 parts of waterwere added. This gives a range of printing pastes of differentviscositles, all of which are found suitable for printing with pigmentsafter the pigment paste is added. If 90 parts of water are added thedispersed lacquer phase is 45.8%. If we use 130 parts of water, thelacquer phase becomes 37.9%. In a similar way the percent soap in thetwo pastes would be 9.9% and 5.6% and when calculated on the waterphases present the monoethanolamine stearate soap would be 12.5 and 9.0%respectively.

The above descriptions and examples are intended to illustrate, thenature of the invention. but the invention is not restricted to theseexamples.

We claim:

1. A self emulsifying base suitable for the formation of an oil in wateremulsion textile printing paste byjdilution with water comprising abinder selected from the group consisting of urea formaldehyde and ethylcellulose 5%, lacquer solvents 77%, a water soluble soap of a g fattyacid of at least twelve carbon atoms 12.18%,

fatty acid of at least sixteen carbon atoms .70%, and water 5.12%.

2. A self emulsifying base suitable for the formation of an oil in wateremulsion textile printing paste by dilution with water comprising ethyl3. A self emulsifying base suitable for the formation of an oil in wateremulsion textile printing paste by dilution with water comprising ureaformaldehyde 5%, pine oil and naptha 77%,

ammonium oleate 12.18%, oleic acid 30%, and water 5.12%.

WILLARD L. MORGAN. NORMAN L. VAUGHN.

